bk-2009-1013.ch011

C h a p t e r 11

Downloaded by COLUMBIA UNIV on June 27, 2012 | http://pubs.acs.org Publication Date: April 27, 2009 | doi: 10.1021/bk-2009-1013.ch011

Advanced Flame-Retardant Epoxy Resins for Composite Materials Michael Ciesielski, Jan Diederichs, Manfred Döring, and Alexander Schäfer Institute for Technical Chemistry, Karlsruhe Research Center, Hermann-von-Helmholtz-Platz 1, D-76344, Eggenstein-Leopoldshafen, Germany

The present article will highlight two different approaches to obtaining phosphorus-modified epoxy materials which are expected to be qualified for high performance printed wiring boards (PWB). The first method involves the incorporation of novel non-reactive derivatives of 9,10-dihydro-9-oxa-10phosphaphenanthrene-10-oxide (DOPO) in an epoxy novolac (DEN 438) and subsequent curing with dicyandiamide (DICY) and fenuron. An alternative process for the manufacture of phosphorus-modified epoxy materials is the reactive introduction (preformulation) of aldehyde adducts of DOPO and 2,8-dimethy 1-phenoxaphosphine-10-oxide (DPPO) into the backbone of the D E N 438 novolac, followed by curing with 4,4`-diaminodiphenylmethane (DDM). The epoxy materials obtained in this way reached the UL 94 V-0 rating at low phosphorus concentrations (0.6-1.4% P) and high T values (180-190 °C). Comparison of the results obtained by both methods, however, revealed a slight superiority of the application of non-reactive additives in the epoxy system used. Whereas all formulations containing aldehyde adducts of DOPO and DPPO exhibited an insignificant drop of T , this parameter was maintained at the high level of the unmodified material when DOPO-based additives bearing bridging and nitrogen-containing substructures were applied. These novel g

g

174

© 2009 American Chemical Society

In Fire and Polymers V; Wilkie, C., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 2009.

175 D O P O derivatives are the first non-reactive additives that do not influence the T of an epoxy material. D E N 438 samples containing commercially available and various other already known organo-phosphorus compounds were manufactured in an analogous manner. A l l of them showed lower T values and poorer flame retardant efficiencies than the novel phosphorus-modified materials. To explain the superior flame inhibition activity of phosphacyclic compounds, the decomposition behaviors of DOPO and DPPO, including their sulfur derivatives, were investigated by means of thermal desorption mass spectroscopy (TDMS) and high-resolution mass spectroscopy (HRMS). PO radicals as well as PS radicals were identified as gas-phase active species. However, such fragments could not be detected when investigating samples containing open-chained phosphorus compounds. g


g

Introduction Electronic devices play an increasing role in our daily life and virtually all electronic items contain a printed wiring board (PWB). Most PWBs are manufactured from copper-clad epoxy-based laminates. However, the flammability of these materials is a crucial disadvantage in electronic and electrical applications. Consequently, many efforts have been undertaken to impart fire retardance to epoxy resins. A widely used approach to rendering epoxies flame-retardant is the incorporation of bromine atoms in their polymeric backbone. Such flameretardant epoxy resins are prepared by a fusion reaction (preformulation) of a brominated aromatic phenol - in most cases tetrabromobisphenol A - with an epoxy compound. Due to ecological and health concerns, however, a general tendency towards banning halogenated fire-retardants is observed. This gives rise to extensive research activities that are aimed at replacing these substances. A n alternative consists in the use of phosphorus-containing additives (1,2% preformulations (3,4) and curing agents (5-11) as flame retardants for P W B materials. O f these, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and its derivatives proved to be very powerful flame retardants in epoxy thermosets (/3, 5-7,12). Normally, non-reactive additives seriously deteriorate the glass transition temperatures (T s) and other material properties of the epoxy thermosets and tend to leach out. The reactive approach solves the migration problem, but in g


176 many cases, the drop of T can not be prevented and additional processing difficulties may occur. This article will start with a survey of phosphorus-containing flame retardants suitable for common PWB-relevant epoxy resins and available today (13). The main part of this study will describe the flame-retardant properties of novel phosphacyclic additives (14) and preformulations (15,16) synthesized by our working group. These derivatives of DOPO and the structural analog compound 2,8-dimethyl-phenoxaphosphine-10-oxide (DPPO) do not or hardly suffer from the abovementioned disadvantages, such that they are expected to be qualified for epoxy resins commonly used in high-performance PWBs. The performances of these DOPO- and DPPO-based additives and preformulations will be compared to those of already reported DOPO-based compounds and commercially available phosphorus-containing flame retardants. The influence of structural parameters of the phosphorus-containing unit on the fire behavior, thermal stabilities, and T values of epoxy materials will be discussed. Crucial importance of tailored chemical structures will be empasized. Furthermore, the results of studies (15,16) of the flame retardant-action of DOPO- and DPPO-derivatives will be presented here. The detection of phosphorus-containing species like the PO radical by means of thermal desorption mass spectroscopy (TDMS) and high-resolution mass spectroscopy (HRMS) will be described and the importance of such radicals to the flame inhibition mechanism will be discussed. This article will be confined to the flame-retardant properties of epoxy samples without glass fibers. The fire behavior of reinforced laminates containing the novel DOPO derivatives will be the subject of investigations in future.


g

g

Halogen-free epoxy materials used in printed wiring boards The National Electrical Manufacturers' Association ( N E M A ) has specified several classes of fire-retardant laminate materials used for PWBs. With approximately 80%, PWBs of the FR-4 classification, made of epoxy resins and reinforced by glass fibers, are most commonly used in the electronic industry. Such materials have to meet special requirements. In particular, they have to obtain the U L 94 V-0 classification that is the most widely used specification for the fire resistance of PWBs. The increasing use of lead-free soldering has changed the P W B base material market. Due to the higher process temperatures of lead-free soldering, there is an increasing demand for P W B laminates of enhanced thermal stability. Often, epoxy-novolac resins are employed for such high-performance base materials of higher glass transition temperatures (Tg > 165 °C). These epoxynovolac resins need less flame retardants compared to the normally used



177 diglycidyl ether of bisphenol-A ( D G E B A ) resins, which makes it easier to meet the technical requirements with halogen-free flame retardants. Use of base materials of higher thermal resistance requires a reformulation of the base material recipes. Many manufacturers have taken this opportunity to investigate halogen-free FRs when developing new materials. Apart from inorganic hydroxides, several organo-phosphorus compounds have already been established as flame retardants for high-performance epoxy materials and represent a growing niche. The chemical structures of commercially available phosphorus-containing fire-retardants suitable for epoxy resins are shown in Figure 1. O f these compounds, aluminium diethylphosphinate is a new nonhalogenated flame retardant that is not hygroscopic, not toxic, has an extremely low solubility in water and common solvents and does not hydrolyze in the presence of water. The latter is most important, since the release of phosphoric acid cannot be tolerated in E & E applications. 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (usually denoted as DOPO) is a commercially available phosphacyclic flame retardant for epoxy resins. Today, DOPO may be regarded as the major building block used to

OH 1

0 1 . ilP - H 0

YS &\ M

o

o

1 OH

DOPO-HQ

DOPO

triphenylphosphate (TPP)

/~\

f

o P-0

Al

3

1*2

bis-phenol A bis(diphenylphosphate) (Fyrolflex BDP°) O n(HO)

O

ii

U

aluminium diethylphosphinate

r

ii

o-P-Ov^^o-p-o C C HH i 3

M

II J

CH

(OH)

m

3

m, n = 0 or 1

poly(l,3-phenylene methyl phosphate) (Fyrol PMP°) Figure 1. Selected commercially available, phosphorus-containing flame retardants for epoxies


178 introduce phosphorus-containing units into epoxy resins (T up to around 160 °C). DOPO is commercially available from different suppliers and global capacities increased over the last five years to meet the increasing market demand for PWBs. DOPO itself is mono-functional towards epoxy groups, but several modifications are commercially available, in particular its Afunctional benzoquinone adduct DOPO-HQ. Poly(l,3-phenylene methylphosphonate) (Fyrol PMP* *) also is a flame retardant especially developed for application in epoxy systems. Due to its hydroxyl groups, it can act as a curing agent for epoxies. This flame retardant is characterized by a high temperature stability. Table I lists the minimum amounts of commercially available flame retardants necessary to achieve the U L 94 V - 0 classification for a typical P W B epoxy formulation, consisting of epoxy novolac resin D O W D E N 438, dicyandiamide (DICY) as hardener, and fenuron as accelerator. The experiments were performed with resins without glass fiber reinforcement. Therefore, these values only indicate the range in a final commercial FR 4 material. g


8

Table I. DOW DEN 438 resin hardened with DICY / fenuron (no glass fiber). Amount of flame retardant necessary for U L 94 V0 classification (13)

-aluminium

-3.2

16.7

UL94 (4 mm) V2 VO

diethylphosphinate Fyrol P M P * DOPO-HQ DOPO DOPO + 30 % boehmite

3.2 1.4 0.93 0.42

23.5 17.0 6.5 2.9

VO VO VO V0

Flame Retardant

Phosphoruscontent (%)

FR-content (%)

Tg(DSC) CO 182 167 165 161 158 168

(Reproduced from reference 13. Copyright 2007.)

Novel Efficient DOPO-Based Flame Retardants Novel DOPO-Based Additives for High-T Epoxy Resins g

DOPO and DOPO-HQ induce excellent flame retardant properties, but they decrease the glass transition temperatures of the epoxy resins. DOPO derivatives which do not show this undesired effect were produced by a novel synthesis route (14) presented in Scheme 1.



179

Scheme 1. Synthesis of the DOPO-basedflame retardants. (Reproducedfrom reference 14. Copyright 2008 John Wiley & Sons, Ltd.)


180 Using this pathway, the already described phosphorus-containing compounds BA-(DOP) and B A - ( D O P ) - 0 (17) as well as the new DOPO derivatives BA-(DOP) -S, DDM-(DOP) , and DDM-(DOP) -S were synthesized. These flame retardants were incorporated in a high-T resin, consisting of an epoxy novolac (DEN 438), D I C Y as hardener, and fenuron. The fire-retardant properties of the DOPO-based additives in this PWB-relevant epoxy resin were evaluated using the U L 94 vertical burning test (14). The fire behavior and thermal properties of triphenylphosphate (TPP) and Fyrolflex BDP® were determinated as well and compared to those of the DOPO derivatives. The minimal phosphorus concentrations necessary to achieve V-0 are summarized in Table II together with the corresponding T values determined by DSC measurements. 2

2

2

2

2

g


g

Table II. Overview of the minimal phosphorus contents necessary to achieve UI 94 VO and the corresponding glass transition temperatures (14) . . Additive in DEN438/DlCr A J J

Min. P content ,. toacheveVO

A

r r n

L4J2

TPP BDP BA-(DOP) BA-(DOP) -S DDM-(DOP) DDM-(DOP)2-S

136 157 164 167 180 184

1.6 2.0 1.0 1.4 0.8 1.2

2

2

2

8

DOW DEN 438 resin hardened with DICY/fenuron (no glass fiber). The preparation and curing of the samples is described in (14). T of the pure DEN 438 sample cured with DICY: 182°C.

b

g

The U L 94 tests revealed that some DOPO-based additives act as superior flame retardants in the D E N 438/DICY resin. The following order of flameretardant efficiencies of the various additives was obtained: D D M - ( D O P ) > BA-(DOP) > DDM-(DOP) -S > BA-(DOP) -S > TPP > B D P > BA-(DOP) -0 2

2

2

2

2

The flame-retardant properties were found to be strongly influenced by the structural features of the additives used. The results of the U L 94 tests showed that nitrogen-containing substituents at the phosphorus atom increase the fireretarding efficiency. Furthermore it was found that DOPO derivatives with trivalent phosphorus are more effective than those with pentavalent phosphorus. Hence, the trivalent DOPO amide DDM-(DOP) is the best fire retardant in the 2


181 D E N 438/DICY resin which required only 0.8% phosphorus to reach V-0. Replacing an oxygen atom by a sulfur atom also has a favorable effect on the flame-retardant properties. These results indicate that the flame-retarding effectiveness of DOPO-based compounds is enhanced with increasing electron density at the phosphorus atom. The influence of the additive and its concentration on the T values for DICY-cured D E N 438 resins is presented in Figure 2.


g

w

*

*

• ^ x

+ BA-(DOP)2 X BA-(DOP)2-0 X BA-(DOP)2-S • DDM-(DOP)2 • DDM-(DOP)2-S • TPP OBDP • DEN438/DICY 0.0

0.5

1.0

1.5 P content [%]

2.0

2.5

3.0

Figure 2. Glass transition temperature versus phosphorus content of DEN 438 samples cured with DICY (Reproducedfrom reference 14. Copyright 2008 John Wiley & Sons, Ltd.)

TPP strongly deterioates the T in the DICY-cured epoxy resin. This result is not surprising, because TPP is a typical non-reactive additive having small molecules with a compact geometry. Fyrolflex BDP® and some DOPO-based additives reduce the T in the epoxy system to a less significant extent only. The molecules of these compounds are elongated compared to those of TPP and have g

g


182 a rod-like geometry. The moderate plasticizing effect of these additives shows that the glass transition temperature is an important material property of epoxy materials that can be maintained at a considerably higher level, i f non-reactive additives having oligomeric, bridging, and rather rigid molecular structures are used. However, DDM-(DOP) , DDM-(DOP) -S and B A - ( D O P ) - 0 exhibited a quite unusual behavior that cannot be expected for non-reactive additives: they did not exhibit any decrease of the glass transition temperature even at high loadings. Figure 3 allows for a direct assessment of the overall performances of the additives used in this study. The minimal phosphorus concentrations necessary to achieve V-0 and the corresponding T values were chosen to be crucial parameters in this


2

2

2

g

• A

+

*

o

A

O

+ BA-(DOP)2 X BA-(DOP)2-S • DDM-(DOP)2 • DDM-(DOP)2-S A DOPO O DOPO-HQ • TPP OBDP - Fyrol P M P — Alumina phosphinate n

U

0.5

1.0 1.5 2.0 2.5 3.0 3.5 Min. P content to achieve UL-94-V0 in DEN438/DICY [%]

Figure 3. Comparison of the overall performances of the DICY-cured samples flame-retardant with various compounds. (Reproducedfrom reference 14. Copyright 2008 John Wiley & Sons, Ltd.)


183 comparison. For a better evaluation, the corresponding values of commercially available phosphorus-containing flame retardants are indicated as well. The DOPO-based additives D D M - ( D O P ) and DDM-(DOP) -S show the highest performances in the epoxy systems used, because they are efficient at very low phosphorus concentrations and do not deteriorate the T values. These novel flame retardants not only surpass the capabilities of all other additives used in this work, but also those of DOPO, DOPO-HQ, and all other commercially available products. 2

2

g

DOPO-Based Preformulations for High-T Epoxy Resins Downloaded by COLUMBIA UNIV on June 27, 2012 | http://pubs.acs.org Publication Date: April 27, 2009 | doi: 10.1021/bk-2009-1013.ch011

g

Various flame-retardant epoxy thermosets with high T s were also obtained by the application of novel reactive DOPO- and DPPO-based flame retardants (15,16): aldehyde adducts of DOPO and DPPO were incorporated in the backbone of a novolac resin ( D E N 438) by fusion reactions according to the synthetic paths shown in Schemes 2 and 3. Preformulations with diethylphosphite -TDA and diphenylphosphite were synthesized in an analogous manner. The phosphorus-containing resins obtained g

2

2R-H

+ \\

O DOP0 -TDA 2

diethylphosphite2~TDA

Scheme 2. Synthesis of phosphorus-containing terephthalaldehyde adducts and subsequent fusion reactions with DEN 438 epoxy novolac.



184

Scheme 3. Phosphorus-containing formaldehyde adducts and subsequent fusion reactions with DEN 438 epoxy novolac.

in this way were cured with 4,4'-diaminodiphenylmethane (DDM). Flammability and burning behaviors of the resultant epoxy thermosets were characterized by U L 94 and LOI and the T s were determined by DSC measurements. The minimal phosphorus concentrations necessary to pass the V-0 rating are summarized in Table III together with the corresponding glass transition temperatures and LOI values at a phosphorus content of 1.7%. All DDM-cured D E N 438 resins with covalently integrated diethylphosphite -TDA and diphenylphosphite units were not classified by the U L 94 vertical burning test up to a phosphorus content of 2%. However, samples with DOPO or DPPO incorporated in the epoxy backbone exhibited superior fire-retardant efficiencies: To achieve the V-0 classification, only 1.4% of phosphorus was necessary in the D P P 0 - T D A based resin. The D O P 0 - T D A containing resin required an even lower phosphorus content (1.0%) to reach the same U L 94 rating. The highest fire-retardant effects, however, were observed in epoxy thermoset samples based on preformulations containing the formaldehyde adducts D O P O - C H O H and D P P O - C H O H . These epoxy resins fulfilled the V-0 classification at phosphorus concentrations of 0.8 and 0.6%, respectively. LOI results confirmed the outstanding fire-retarding effectiveness of covalently bound DOPO and DPPO derivatives in the epoxy system investigated. D E N 438 resins incorporating DOPO-based flame retardants showed high oxygen indices of up to 33% 0 at a phosphorus content of 1.7%, while DPPO-based resins exhibited LOI values of up to 31% at comparable phosphorus contents. A l l formultions containing aldehyde adducts of DOPO and DPPO exhibited an insignificantly drop of T . This parameter is maintained at a high level of 180200 °C at the phosphorus contents necessary to achieve V-0. g

2

2

2

2

2

2

g


185 Table III. Overview of the fire behaviors and glass transition temperatures of phosphorus-containing DDM-cured DEN438 epoxy novolac resins Min. P content to achieve VO (%P) not rated 1.0

Formulation" DEN438/DDM DOPO TDA DEN438/DDM DPPO TDA DEN438/DDM diethylphosphite TDA DEN438/DDM DPPO-CH OH DEN438/DDM DOPO-CH OH DEN438/DDM diphenylphosphite DEN438/DDM r


r

2

2

2

T (°C) at the min P content to achieve VO g

—

LOI (% O2) at 1.7% P

189

26.5 33.1

1.4

185

27.2

not rated

-

25.7

0.6

199

31.1

0.8

183

31.5

not rated

-

27.3

* Neat resin (no glass fiber). The formulation and curing procedures are described in (15, 16).

Mechanistic Studies to the Flame Retarding Process in Epoxy Resins These experiments were aimed at identifying the active species resonsible for the flame-retarding process and explaining the differences in the fireredardant efficiencies of heterocyclic and open-chained phosphorus compounds. Possible modes of action of flame retardants include charring, intumescence (both in the solid phase), and flame inhibition by radical species (in the gas phase). To detect gas-phase active decomposition products, the pyrolysis gases of cured resins with and without flame retardants were analyzed by means of T D M S (7(5). M S investigations may provide an idea of possible products formed during the thermal decomposition of a substance. Powdered samples of the cured resins (10-20mg) were heated in a highvacuum system (10" hPa) from room temperature to 460 °C at a heating rate of lOK/min and the pyrolysis gases were analyzed by T D M S . The results of these investigations are presented in Figure 4. H R M S measurements revealed that the decomposition of DOPO and DPPO starts with the cleavage of the P-H bond (see Scheme 4) (75). In the following 8


186 3.01E-10

DOPO2 -TDA -DEN-DDM

2.01E-10 2 Downloaded by COLUMBIA UNIV on June 27, 2012 | http://pubs.acs.org Publication Date: April 27, 2009 | doi: 10.1021/bk-2009-1013.ch011

CO

a JS

1.01E-10 DPPO2 -TDA - D E N - D D M DEPP2 - T D A - D E N - D D M

virgin D E N - D D M

1EM2 50

150

250 350 Temperature [°C]

450

Figure 4. Thermal desorption mass spectrometry of epoxy novolac samples preformulated with different P-containing terephthaldialdehyde derivatives, cured with DDM - PO detection. (Reproducedfrom reference 16. Copyright 2007 Wiley Periodicals, Inc.)

fragmentation step, a dibenzofiiran system is formed and the PO radical is released. Results of density functional theory (DFT) calculations confirmed this decomposition route shown in Scheme 5 and excluded an alternative route which would involve the direct break-up of the phosphacycle into dibenzofiiran and a HPO fragment. The thermal decomposition behavior of epoxy samples containing sulfursubstituted DOPO derivatives were investigated in the same manner. In this case, PS radicals as the possible gas phase-active species were detected instead of POfragments. Until now, PO and P X radicals have only been detected in the decomposition gases of DOPO- and DPPO-containing polymers. Further studies



187

Scheme 4. Possible decomposition behaviors of DOPO and DPPO



188

Scheme 5. Calculated reaction energies (DFT)

are now in progress to reveal i f such or related fragments are also responsible for the flame inhibition activity of other phosphorus compounds.

Conclusions Two approaches to obtaining phosphorus-modified epoxy materials with glass transition temperatures around 180 °C and the U L 94 rating V-0 were presented. The first involved the addition of non-reactive DOPO derivatives to an epoxy novolac (DEN 438) and the subsequent curing with DICY/Fenuron. The second approach was based on the reactive introduction (fusion reaction) of aldehyde adducts of DOPO and the structurally similar phosphacycle DPPO into the backbone of the epoxy novolac. D D M was used as curing agent in this case. Surprisingly, the comparision of the results obtained revealed the superiority of the former approach in the epoxy system used: the application of non-reactive additives having tailored chemical structures. Especially DOPO amides with two DOPO units per molecule exhibited outstanding properties. These novel additives were found to be powerful fire retardants in the D E N 438/DICY resin. Only 1% phosphorus was necessary to obtain the U L 94 V-0 classification. The most important fact, however, is that these novel DOPO derivatives are the first non-reactive additives known which do not deteriorate the glass transition temperature. Hence, the T as a crucial material parameter can be maintained at the high level of the pure resin, i f non-reactive phosphorus compounds having bridging and rather rigid structures are used. High-performance epoxy materials with the U L 94 V-0 rating at low phosphorus concentrations (0.6-1.4% P) were also obtained by the g


189 preformulation of aldehyde adducts of DOPO and DPPO with DEN 438 and curing with DDM. However, a slight drop of the T could not be prevented by this approach. Comparison of the results for our novel compounds with those of samples containing open-chained and commercially available fire retardants revealed that some of the new DOPO and DPPO derivatives have an outstanding performance. Furthermore, a general superiority of phosphacyclic flame retardants compared to open-chained ones was observed in the novolac-based epoxy matrix used. Investigations by means of TDMS and HRMS provided an idea of the reason of this difference in flame-retardant efficiencies. Whereas the phosphacyclic compounds showed a significant release of small phosphoruscontaining fragments (PO and PS radicals) which can inhibit the burning process, such species could not be detected if the open-chained compound and the virgin resin was investigated. Due to their outstanding properties some of the novel phosphacyclic fire retardants described in this study are expected to be qualified for resins in advanced composites commonly used in high-performance PWB.


g

References 1. 2.

3. 4. 5. 6. 7.

8. 9. 10. 11. 12. 13.

Perez, R. M.; Sandler, J. K. W.; Altstädt, V.; Hoffmann, T.; Pospiech, D.; Ciesielski, M.; Döring, M. J. Mater. Sci. 2005, 40, 341-353. Perez, R. M.; Sandler, J. K. W.; Altstädt, V.; Hoffmann, T.; Pospiech, D.; Ciesielski, M.; Döring, M.; Braun, U.; Knoll, U.; Schartel, B. J. Mater. Sci. 2006, 41, 4981-4984. Wang, C.-S.; Lee, M.-C. Polymer 2000, 41, 3631-3638. Jain, P.; Chaudary, V.; Varma, I. K. J. Makromol. Sci.-Polym. Rev. 2002, 42, 139-183. Lu, S.-Y.; Hamerton, I. Prog. Polym. Sci. 2002, 27, 1661-1712. Lin, C. H.; Cai, S. X. J. Polym. Sci. Al. 2005, 43, 5971-5986. Artner, J.; Ciesielski, M.; Walter, O.; Doering, M.; Perez, R. M.; Sandler, J. K. W.; Altstaedt, V.; Schartel, B. Macromol. Mat. and Eng. 2008, 293, 503514. Liu, Y.-L.; Hsiue, G.-H.; Lee, R.-H.; Chiu, Y.-S. J. Appl. Polym. Sci. 1997, 63, 895-901. Liu, Y.-L.; Hsiue, G.-H.; Chiu, Y.-S. J. Polym. Chem. 1997, 35, 565-571. Shieh, J.-Y.; Wang, C.-S. J. Appl. Polym. Sci. 2000, 78, 1636-1644. Hergenrother, P. M.; Thompson, C. M.; Smith, J. G.; Connell, J. W.; Hinkley, J. Α.; Lyon, R. E.; Moulton, R. Polymer, 2005, 46, 5012-5024. Levchic, S. V.; Weil, E. D. J. Fire Sci. 2006, 24, 345. Döring, M.; Diederichs, J. Halogen-freeflameretardants in E&E applications, Karlsruhe Research Center, Karlsruhe 2007, www.halogenfree-flameretardants.com.


190


14. Ciesielski, M.; Schäfer, Α.; Döring, M. Polym. Adv. Technol. 2008, 19, 507515. 15. Schäfer, Α.; Seibold, S.; Lohstroh, W.; Walter, Ο.; Döring, M. J. Appl. Polym. Sci. 2007, 105, 685-696. 16. Seibold, S.; Schäfer, Α.; Lohstroh, W.; Walter, Ο.; Döring, M. J. Appl. Polym. Sci. 2008, 108, 264-271. 17. Su, W.-C; Sheng, C.-S. U.S. Patent 0,101,793A1,2005.


bk-2009-1013.ch011

Recommend Documents